Spotting Solid Oxide Fuel Cell Degradation Effects by Electron Microscopy

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 - August 2, 201

TEM investigation on zirconate formation and chromium poisoning in LSM/YSZ cathode

Cell durability is a crucial technological issue for SOFC commercialization, and considerable progress has been made in recent years. A number of degradation pathways have been established, amongst which microstructural changes, poisoning effects and formation of less conductive phases. In this study, transmission electron microscopy was used to observe submicron-scale effects on selected cathode zones of an anode supported cell tested in SOFC stack repeat element configuration. The test has been performed with a dedicated segmented test bench, at 800°C for 1900h, which allowed to spatially resolve degradation processes, and therefore to improve their correlation with localized post-test analysis. Evidence is presented of reaction products (mainly SrZrO3) at the LSM/YSZ interfaces as well as of contaminants, in particular Cr, but also Si. A polarized cell segment is compared to an unpolarized one, to assess any influence of cathode polarizatio

Physically-based deconvolution of impedance spectra for LSCF-based SOFC

A physically-based model for the interpretation of the impedance spectra of an anode-supported LSCF/GDC/YSZ/Ni:YSZ solid oxide fuel cell is presented in this work. The model locally describes transport and reaction phenomena within the cell components through mass conservation equations. The microstructural properties of the electrodes are predicted through numerical three-dimensional reconstruction of the microstructure, with input parameters obtained from the analysis of SEM pictures of each layer. Simulations show that the model reproduces impedance spectra obtained in different operating conditions with the same set of fitting parameters, comprising material-specific kinetic constants and electrochemical capacitances, which fairly agree with independent literature data and a previous analysis of the spectra through DRT. The model allows for the deconvolution and quantification of the characteristic resistance and frequency of the different physical processes that build up the impedance of the cell. In particular, 7 processes are identified: charge-transfer reactions between LSCF/GDC, GDC/YSZ and Ni/YSZ interfaces appear in the high-frequency range, the medium-frequency feature is due the oxygen reduction reaction and the gas diffusion in the anode, while the low-frequency arc is mainly due to the gas conversion in the anodic channel. An additional low frequency contribution (< 1Hz), not considered in the model, is observed and tentatively attributed to the adsorption of oxygen onto the LSCF surface. Simulation results suggest that more efforts must be dedicated to characterize and improve the oxygen transfer at the LSCF/GDC and GDC/YSZ interfaces. The study shows that a quantitative interpretation of impedance spectra is possible with a reduced number of fitting parameters when a physically-based approach is adopted, making the model an attractive tool for diagnostic purposes

Aging of materials at inlet and outlet fuel manifolds in a SOFC stack

Analyses performed on a stack operated for more than 4000h at 750\ub0C at high fuel utilization (80%) revealed significant differences in aging behaviour of stack components when comparing fuel inlet and fuel outlet areas. Two samples were cut from the fuel inlet and outlet manifolds of the operated SOFC stack. The glass-ceramic sealing material and the interconnect alloy were exposed to a dual atmosphere (external air and internal fuel stream). The fuel composition was dry H2/N2 (60:40 vol. %) at the inlet and H2O/H2/N2 (48:12:40 vol. %) at the outlet. The stack was operated in co-flow configuration, with a large excess of air. It was found that the interfaces between the seal and the alloy were significantly affected by the difference in fuel composition. The sealant exposed to the outgoing air was significantly polluted by chromium generated in the stack and transported by the air stream. These investigations therefore reveal that the long-term evolution of the sealing and of the metallic support depends on the local conditions in the stack, as well as on additional interactions with other degradation phenomena

Production and reliability oriented SOFC cell and stack design

The paper presents an innovative development methodology for a production and reliability oriented SOFC cell and stack design aiming at improving the stacks robustness, manufacturability, efficiency and cost. Multi-physics models allowed a probabilistic approach to consider statistical variations in production, material and operating parameters for the optimization phase. A methodology for 3D description of spatial distribution of material properties based on a random field models was developed and validated by experiments. Homogenized material models on multiple levels of the SOFC stack were established. The probabilistic models were related to the experimentally obtained properties of base materials to establish a statistical relationship between the material properties and the most relevant load effects. Software algorithms for meta models that allow the detection of relationships between input and output parameters and to perform a sensitivity analysis were developed and implemented. The capabilities of the methodology is illustrated on two practical cases

Simulation of thermal stresses in anode-supported solid oxide fuel cell stacks. Part I: Probability of failure of the cells

Structural stability issues in planar solid oxide fuel cells arise from the mismatch between the coefficients of thermal expansion of the components. The stress state at operating temperature is the superposition of several contributions, which differ depending on the component. First, the cells accumulate residual stresses due to the sintering phase during the manufacturing process. Further, the load applied during assembly of the stack to ensure electric contact and flatten the cells prevents a completely stress-free expansion of each component during the heat-up. Finally, thermal gradients cause additional stresses in operation. The temperature profile generated by a thermo-electrochemical model implemented in an equation-oriented process-modelling tool (gPROMS) was imported into finite-element software (ABAQUS) to calculate the distribution of stress and contact pressure on all components of a standard solid oxide fuel cell repeat unit. The different layers of the cell, i.e. anode, electrolyte, cathode and compensating layer were considered in the analysis by using the sub-modelling capabilities of the finite-element tool. Both steady-state and dynamic simulations were performed, with an emphasis on the cycling of the electrical load. The study includes two different types of cells, operation under both thermal partial oxidation and internal steam-methane reforming and two different initial thicknesses of the air and fuel compressive sealing gaskets. The results generated by the models are presented in two papers: Part I, focuses on the assessment of the risks of failure of the cell, which was performed by Weibull analysis, while the issues related to the other components are discussed in Part II. Only the anode support contributed to the probability of failure, since the other layers underwent compressive stresses independently of the operating conditions. The cell at room temperature after the reduction procedure was revealed as a critical case. Thermal gradients and the shape of the temperature profile generated during transient operation induced high probabilities of failure. The computed reliability is incompatible with commercialisation, but the scatter induced by the experimental data covers several orders of magnitude. Alternatively, the computed required strength of the anode material to fulfil a probability of failure of 10−2 in a 50-cells stack during steady-state operation appears achievable. Finally, extreme care is required when using the maximum thermal gradient or temperature difference over the SRU as an indicator for cell cracking

Fast RTO Applied to a Commercial SOFC System

The experimental implementation of real-time optimization (RTO) to a commercial solid-oxide fuel-cell (SOFC) system is reported in this paper. The goal of RTO is to maximize the system efficiency at steady state subject to several operating constraints. The proposed RTO strategy is a constraint-adaptation approach, which consists in adding bias correction terms to the constraints in the optimization problem. These bias terms are estimated during operation using transient measurements in combination with a dynamic model. The scheme enforces plant optimality by continuously detecting and tracking the set of active constraints. This approach drives the fuel-cell system quickly to the desired power demand, while maximizing the efficiency and paying attention to constraint satisfaction. As such, this RTO scheme has the ability to both control and optimize fuel-cell systems. This experimental system reached about 65% efficiency. In addition, it was possible to deal with slow drifts such as degradation without compromising on optimality. (C) 2019, IFAC (International Federation of Automatic Control) Hosting by Elsevier Ltd. All rights reserved